Composition of matter and method of making same



atented Fe. 26, id

I UNiTE comesrrron or MATTER AND ME'rnon or r c s Melvin De Groote,University City, Mo., assignor to Petroilte Corporation, Ltd.,Wilmington, DeL, a corporation of Deiaware No Drawing.

1941, Serial No.

Original application September 8,

410,084. Divided and this appiication June 21, 1943, Serial No. 491,730

7 Claims.

This invention consists of a new composition of matter and a method ofmaking same, my present application being a division of my pendingapplication Serial No. 410,084, filed September 8, 1941, which maturedas U. S. Patent No. 2,342,650, dated February 29, 1944, and which inturn, was a continuation in part of the application that resulted in myU. S. Patent No. 2,262,741, dated November 11, 1941.

My said Patent No. 2,262,741, discloses a process for preventingwater-in-oil type emulsions resulting from acidization of calcareousoilbearing strata, wherein the treating agent employed is. a compositionof matter consisting of a mineral acid, such as hydrochloric acid, inadmixture with a particular emulsion-preventing agent that isspecifically described in said patent. In said patent theemulsion-preventing agent is referred to, in view of the most suitablemethod of manufacture, as a condensation product. Attention is directedto the aforementioned patent to the extent that said patent isconcerned, not only with a description of certain cation-activematerials, but also to the extent that said patent indicates utility forsuch materials, as, for example, in demulsiflcation of crude petroleumor of similar procedure involving the removal of salt in refiningpractice.

The subject-matter of the instant specification is substantially averbatim copy of the subject-matter appearing in my said Patent No.2,262,741, except that there is eliminated such data as is concernedprimarily with acidization of calcareous structures, and reference tothe matter contemplated is as a condensation product, chemical product,or the like, rather than specific reference to it as anemulsion-preventing agent.

The condensation product or chemical compound that constitutes mypresent invention is obtained by reaction between a higher molecularweight monocarboxy acid or its functional equivalent, and a polymerizedpolyamine derived from a hydroxylated polyamine containing at least onenitrogen atom not directly linked to a hydroxy hydrocarbon radical, andpreferably, at least two amino nitrogen atoms not directly linked to ahydroxy hydrocarbon radical. Such reactants are mixed together so thatthere is at least one mole of the high molal carboxy acid for each moleof polymerized hydroxylated polyamine; and there may be several moles ofsuch high molal carboxy acid combined with each mole of the polymerizedhydroXylated amine.

.to approximately 0.1%, or even less.

the heat generally at a temperature above 100 C., and may be conductedat'a temperature as high as 300 C. Generally speaking, the range of150-175" C. represents an optimum temperature. I Preferably,condensation is conducted by first polymerizing such hydroxylated aminesand then condensing the polymerized hydroxylated polyamine with theselected acid. Polymerization catalysts consist of materials of the kindcommonly employed to polymerize hydroxylated monoamlne, such astriethanolamine. They include materials such as caustic soda, causticpotash, high molal amines, soaps, sodium glycerate, sodium methylate,sodium ethylate, and the like. The amounts used vary from 1%Polymerizatlon'is generally conducted at a temperature range ofapproximately 225-275 C. Constant stirring is desirable duringpolymerization, and condensation. Such condensation products are usuallycation-active materials. h

The detailed composition of the products obtained is not known,although, in a general Way,

ester linkages must be involved.

As indicated, an amine may act as a catalyst; or, stated another way,the hydroxylated amine of the kind employed as a reactant in theproduction of the emulsion-preventing agent or condensation product, mayact as its own polymerization catalyst. For instance, in condensationproduct Examples 1-8, inclusive, as described subsequently, the addedcatalyst may be eliminated or reduced, with probable increased time ofcondensation being required. Thus, in the hereto appended claims,reference to a catalyst is intended to include the amine itself, as wellas an added catalyst, if employed. For

- this reason many of the properties of the materials are unpredictable.

It is surprising to find that such materials are stable for an extendedperiod of time in halfconcentrated hydrochloric acid, or other similarmineral acids. It is likewise remarkable to note that such solutions inacid, and particularly in relatively low ratios, as hereinafterdescribed, give a very pronounced lowering of the surface tension. Thisis especially true in such compounds or condensation products that arederived at relatively high temperatures, and especially if derived frompolyamino reactants, having at least two amino nitrogen atoms notdirectly linked'to a hydroxy hydrocarbon radical. It is diflicult toindicate a detailed probable Such condensation is effected by the actionof 55 structure for such comp u hi o d a count for their resistance todecomposition in strong acid solution.

Materials of the kind herein contemplated are derived from variousreactants. One class of reactants consists of higher molecular weightcarboxy acids, and particularly monocarboxy acids or their functionalequivalents, such as the acyl halide, ester, amide, etc. The expressionhigher molecular weight carboxy acids is an expression frequentlyemployed to refer to certain organic acids, particularly monocarboxyacids, having more than 8 carbon atoms, and generally less than 40carbon atoms. The commonest examples include the detergent-formingacids, 1. e., those acids which combine with alkalies to produce soap orsoap-like bodies. The detergentforming acids, in turn, includenaturally-occurring fatty acids, resin acids, such as abietic acid,naturally-occurring petroleum acids, such as naphthenic acids, andcarboxy acids produced by the oxidation of petroleum. As will besubsequently indicated, there are other acids which have somewhatsimilar characteristics and are derived from somewhat different sourcesand are different in structure, but can be included in the broad genericterm previously indicated.

Among sources of such acids may be mentioned straight chain and branchedchain, saturated and unsaturated, carboiwlic, aliphatic, alicyclic,fatty, aromatic, hydroaromatic, and aralkyl acids, including caproicacid, capric acid, pimelic acid, sebacic acid, erucic acid, saturatedand unsaturated higher molecular weight aliphatic acids, such as thehigher fattyacids containing at least 8 carbon atoms, and including, inaddition to those mentioned, melissic acid, stearic acid, oleic acid,ricinoleic acid, diricinoleic acid, triricinoleic acid, polyricinoleicacid, ricinostearolic acid, ricinoleyl lactic acid, acetylricinoleicacid, chloracetyl-ricinoleic, acid, linoleic acid, linolenic acid,lauric acid, myristic' acid, undecylenic acid, palmitic acid, mixturesof any two or more of the above mentioned acids or other acids, mixedhigher fatty acids derived from animalor vegetable sources, for example,lard, cocoanut oil,

rapeseed oil, sesame oil, palm kernel oil, palm oil,

olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil,peanut oil, castor oil, seal oils, whale oil, shark oil, and other fishoils, teaseed oil, partially or completely hydrogenated animal andvegetable oils, such as those mentioned; hydroxy and alphahydroxy highercarboxylic aliphatic and fatty acids, such as dihydroxystearic acid,dihydroxy palmitic' acid, dihydroxybehenic acid, alphahydroxy capricacid, alyphahydroxy lauric acid, alphahydroxy myristic acid,alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margaric acid,alphahydroxy arachidic acid, and the like; fatty and similar acidsderived from various waxes, such as beeswax,

spermaceti, montan wax, Japan wax, coccerin,

and camauba wax. Such acids include carbaubic acid, cerotic acid,lacceric acid, montanic acid, psyllastearic acid, etc. As suggested, onemayalso employ higher molecular weight carboxylic acids derived, byoxidation and other methods, from paraflin wax, petroleum and similarhydrocarbons; resinic and hydroabietic acid, aralkyl and aromatic acids,such as benzoic acid, Twitchell fatty acids, naphthoic acid.carboxydiphenyl pyridine .carboxylic acid, hydroxybenzoic acid, and thelike. Other suitable acids include phenyl- Insofar that the fatty acidsare preferably employed as a sourceof the acyl radical, obviously oneneed not use the fatty acids themselves, but may employ any obviousfunctional equivalent, such as an ester, anhydride, amide, acyl halide,etc. It is understood that in the hereto appended claims reference toformation of a condensation product being derived from an acid isintended to by the presence of at least one amino nitrogen atom notdirectly attached to a hydroxy hydrocarbon radical, are well knowncompounds. They may be obtained in various ways. The commonest procedureis to treat a polyamine with an alkylene oxide or its equivalent, suchas ethylene oxide, propylene oxide, glycidcl, or the like. The

. commoner polyamines which can be so treated stearic acid,benzoylnonylic acid, cetyloxyacetic acid, chlorstearic acid, fencholicacid, cetyloxybutyric acid, etc.

with an oxyalkylating agent include the following: Ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene -pentamine,pentaethylene hexamine, propylene ,diamine, dipro'pylene triamine,tripropylene tetramine, tetrapropylene pentamine, pentapropylenehexamine,

etc. In some instances such. amines may be treated with an alkylatingagent or the like so as to introduce an alkyl, aralkyl, or alicyclicradical into the compound as a substitute for an amino hydrogen atom.For instance,one may obtain diethyl tetraethylene pentamine in theconventional manner, using ethyl iodide or the like as an alkylatingagent.

In any event, having selected a suitablepolyamine, the product is thentreated with any acceptable oxyalkylating agent, such as ethylene oxide,propyleneoxide, and the like. In view of the lower cost .of ethyleneoxide, and in view of its greater activity, it is most frequentlyemployed. For instance, ethylene diamine can be treated with one mole ofethylene oxide to produce hydroxyethyl ethylene diamine. -Diethylenetriamine can be treated with threemoles of ethylene oxide so as to yieldtriethanol diethylene triamine. Triethyl'ene tetramine can be treatedwith four moles of. ethylene oxide to yield tetraethanol 'triethylenetetramine. Similarly, one can obtain tetraethanol .tetraethylenepentamine, or tetraethanol"pentaethylene hexamine. One can employpropylene oxide or glycidol to give similar products. In view of thefact that the most inexpensive polyamine now available is tetraethylenepentamine, I prefer to treat tetraethy-lene pentamine with three moles,four moles, or five moles of ethylene oxide to give the correspondingtriethanol, tetraethanol, and pentaethanoi derivatives and to employsuch derivatives. f

In the manufacture of the emulsion-preventing agent or condensation;agent herein described, it is sometimes desirable to add a polyhydricalcohol, such as glycerol, ethylene glycol, diethylene glycol,diglycerol, propylene glycol, or the like. The effect of adding suchpolyhydric alcohol is essentially the same efiect as would be obtainedby treating the high molal alcohol with an alkylene oxide, such asethylene oxide, propylene oxide,

treating the polymerized hydroxylated amine in a kindred fashion.

In view of the numerous reactants which have been indicated, it isobvious that one can obtain a variety of condensation products oremulsionpreventing reagents. It a compound or emulsion-preventing agentis not soluble enough, its solubility, or the solubility of its salt,can be increased in various manners, for instance:

(a) Employ a monocarboxy acid "having a lower molecular weight;

(b) Use fewer moles of acid per mole of original unpolymerizedpolyamine;

() Select as a raw material an amine having a greater number of aminonitrogen atoms;

(d) Select as a raw material an amine having a greater number of hydroxyhydrocarbon radicals;

(e) Select as an amine a compound having both an increased number ofnitrogen atoms and an increased number of hydroxy hydrocarbon activityfor the purposeintended. In such instances it may be desirable todecrease the hydrophile properties. It is unnecessary to remarl: thatthis requires only a reversal of one or more of the procedurespreviously enumerated. It is believed that in view of what hasbeen'said, the compounds oi the kind contemplated can be preparedwithout further directions or illustrations. However, for the purpose-ofindicating the preferable type of condensation product oremulsion-preventing agent, attention is directed to the followingexamples:

Polrmerised hydroeylated polyomine- Example 1 Triethylene tetrarnine istreated with four moles of ethylene oxide to produce tetraethanoltriethylene tetramine. Approximately threefouiths of a percent ofcaustic soda is added to this material by weight and the hydroxylated aeis heated for approximately two to four hours at about 2d5-260" C. Themass is stirred constantly and any distillate is condensed and reservedfor re-use after an intermediate rern step. As polymerization takesplace, as indicated by elimination of water and increase in viscosity ofthe residual mass, cryoscopic molecular weight determinations are madeon the polyamlne or a suitable salt, such as the acetate. or the like,and polymerization is stopped when such molecular weight determinationsindicate that the material based on average values is largely dimeric.

The reaction with ethylene oxide may be indicated in the following '-i a1- NCsHtNCzHrNCsHa CIHIOH It the above formula be rewritten as no on \R/in which R represents the tetravalent radical to which the fourhydroxyls are attached, then the simplest linear condensation reactionis indicated in the following manner:

OH HO OH ogsles'g cognizance must betaken of the fact that cyclicstructures may form, asindicated by the following possible reaction:

Additionally combined cyclic and acyclic forms may appear.

Polymer-iced hydrozylated polyamina- Example 2 The same procedure isemployed as in the previous example, except that heating is conductedfor approximately 1-3 hours longer. Tests are made in the same manner aspreviously indicated, and polymerization is stopped when determinationsindicate that the average molecular weight is equivalent to a trimericproduct.

Polymerized hydroaylated miserable.-

Example 3 The same procedure is followed as in mample 2, preceding,except that a slightly higher temperature is employed, i. e., about 10higher, and if need be, a slightly longer time; and the process iscontinued until the, product indicates an average molecular weight equalto or exceeding that of a tetramer,

Polymerized hydrorylated polyamine.--

Example 4 The preceding examples are repeated, adding one moleofglycerol for each mole of hydroxylated amine employed.

Polymerized hydroxylated pole/amine.-

Eeample 5 Examples 1-3, inclusive, are repeated, adding two moles ofglycerol for each mole of hydroxylated polyamine employed Polymrizedhydroaylated POZZiamiM.- Example 6 Tetraethanol pentaethylene hexarnineis substituted for tetraethanol triethylene tetramine in Examples 1-5.

Polymerized hydroxylated polyamine- Ezample 7 Tetraethanol tetraethylenepentamine is substituted for tetraethanol pentaethylene hexamine in thepreceding example.

Polymerized hydromylated nob/amine.- Example 8 4 .1 assasoo Polymer-teedhudrocylatedpolyamina- Condensation product-Example 3 Example 9 7 Oleicacid is used instead of ricinoleic acid in I Hexa-ethanoltetraethylenepentamina is sub- Examples 1 and 2, preceding, stituted for pentaethanoltetraethylene pentaamnion woductz zxample d-$ 5,2 5: 22 m; 335 L t poly-Abietic acid is used instead of ricinoleic acid merized hydrcxylatedamine and the high molal in males 1 nd 2, p c din I carboxy acid or itsequivalent, are prepared in condensation moduct Ezample 5 such ratiothat there is present at least one mole m of the high molal fatty acidor its equivalent for each mole of polymerized amine. My preferenceNaphthenic acid is used instead of ricinoleic acid in Examples 1 and 2,preceding.

is to use a dimeric, trimeric, or tetramerio form Condensationproduct-Example 6 the wlymmzed hydmxylated m The exmm ples of the typepreviously indicated preference also is to use a fatty acid, rather thanany other type of monocarboxy acid, and particularly to employunsaturated fatty acids, such as molal a G1 (L sonebean fatty acids,teaseed ell i'atty acids, corn oil fatty acids, and the like. Theglteiirn- Condensation product-Example 7 able mtmted fatty acid appearsExample 5 is remated, using two pound moles acid- It is usedif desiredin a more avail of glycerol in each instance instead of one pound ableform, to wit, the glyceride. In 031:1 words, mole.

in subsequent Example 1 and succee g examples, it is really preferableto substitute one. condensation Product-Example 3 pound mole oftriricinolein (castor oil) for three Examples 1-7, preceding, arerepeated, using pound moles of ricinoleic acid. polymerized hydroxylatedpolyamines, Examples The temperature of condensation has previ- 2-9,instead of Example 1, as in the previous exare repeated, with theaddition of one pound ously been indicated. In a general way, it isamples.

above 100 0.; but any temperature below the Inthe hereto appendedclaims, reference to the point of decomposition of the hydrotropicconuse of the condensation product is intended to densation materialsmay be employed. Although I include the base form, 1. e'., the chemicalcombithe preferred range indicated in succeeding exnation of water, andalso the salt form such as amples is 150-1'75 0., in many instances verythe lactate, acetate, citrate, or the like.

valuable reagents are obtained by using a con- It has been previouslypointed out that a large siderably higher temperature, to wit, 250-300C. variety 'of the materials herein described represents surface-activematerials, or more specondensafim product-Exam? 1 ciflcally,cation-active materials. There is a A mixture is prepared, using onepound mole wide variety of uses for surface-active materials.

each of the following: Ricinoleic acid and a ma- See, for example, U. S.Patent No. 2,174,181,

terial of the kind exemplified by polymerized hy- 0 dated September 26,1939, to Lubs. Some of mole of glycerol for each pound mole of the highdroxylated polyamine, Example 1. The products these purposes areparticularly adapted to the l are mixed and stirred constantly, holdingthe use of a cation-active material, or a cationtemperature atapproximately 150-175" (3., until active material which is at leastself-emulsifiable. no unreacted high molal acid remains. The bulkBriefly, then, specific uses for my product inof such high molal acidgenerally disappears clude use as wetting, detergent, and levelingwithin two to three hours; but sometimes it is agents in the laundry,textile, and dyeing indusnecessary to heat from 4 to 6, or even 10,hours. try as wetting agents and detergents in the acid toobtainsubstantially complete reaction. The washing of fruit and in the acidwashing of final-completion of reaction is indicated in varbuildingstone and brick; as a' wetting agent ions ways, and usually by the factthat the prodand spreader in the application of asphalt in not gives aclear solution in dilute acetic acid. road building and the like; as aconstituent of The simplest aspect of the dimeric compound solderingflux preparations; as a flotation reillustrating polymerizedhydroxylated polyamine agent in the flotation separation of variousminis indicated by the following: erals; for flocculation andcoagulation of var- 1100 c eg 5350 c on n n. n n .N/

NCIHiNClHNCsH CS lNCSHANQi HOCsHs CaHiQH HOCsHi OSHIOH Ricinoleic acidmay be indicated by the formula 60 ions aqueous suspensions containingnegatively RCGOH. Acylation would preferably involve an chargedparticles such as sewage; coal washing amino hydrogen atom(amidiflcation), rather waste water, and various trade wastes and thethan a hydroxyl hydrogen atom (esteriflcation). like; as germicides andinsecticides; and emul- Thus, the probable reaction which takes placeinsiflers for cosmetics, spray oils, water-repellent volving theprevious compound so as to form an textile finish, etc. These uses areby no means amide, is indicated inthe following manner: exhaustive. Theproducts may be used as demulsiflers in the manner that such materialsrare most widely used in the production of crude 3 oil or removal ofsalt in refinery practice.

10 Products of the kind herein contemplated may be considered asintermediate products and may condensation ze be reacted with othermaterials, particularly dim I p a basic acids, or fractional salts oresters thereof.

One pound mole of ricinoleic acid in Example such as oxalic acid, maleicacid, phthalic acid.

1 above is replaced by two pound moles. 1s oxalic acid, sodium acidphthalate, octyl acid phthalate, triricinolein monophthalate,triricinolein diphthalate, and the like, to give valuable products whichmay be used for the various purposes enumerated in the precedingparagraph.

I have found that the particular chemical compounds or reagents hereinemployed as emulsion-preventing agents may also be used for otherpurposes, for instance, as a break inducer in doctor treatment of thekind intended to sweeten gasoline. See U. S. Patent No. 2,157,223, datedMay 9, 1939, to Sutton.

Having thus described my invention, what I claim as new and desiretosecure by Letters Patent is: t

1. A polymerized condensation product, obtained by heat polymerizationin presence of an alkaline catalyst from (A) A hydroxylated polyethyleneamine having atv least 3 amino nitrogen atoms and not more than 6 aminonitrogen atoms and having 2 hydroxyalkyl radicals attached to each ofthe 2 terminal amino nitrogen atoms and with the proviso that at least 1of the intermediate nitrogen atoms be part of a secondary amino group;and

' (B) At least 1 mole of a high molecular weight monocarboxy acid havingat least 8 carbon atoms; said polymerized condensation productcontaining a plurality of H radicals, in which n is a whole number from1 to 4 and the acyl radical of the said high molecular weightmonocarboxy acid is amido-linked to an intermediate nitrogen atom andsaid plurality of polyamino radicals are ether-linked to each other.

V 2. The condensation product of claim 1, wherein the higher molecularweight monocarboxy acid is a fatty acid.

3. The condensation product of claim 1, wherein the higher molecularweight monocarboxy acid is an unsaturated fatty acid.

4. The condensation product of claim 1, wherein the higher molecularweight monocarboxy acid is an unsaturated fatty acid, and n is 2.

5. The condensation product of claim 1, wherein the higher molecularweight monocarbozgy acid is an unsaturated fatty acid, and n is 6. Thecondensation product of claim 1, wherein the higher molecular weightmonocarboxy acid is an unsaturated fatty acid, and n is 4.

7. A method for the manufacture of the polymerized condensation product,as defined in claim 1, involving the step of heat polymerization inpresence of an alkaline catalyst; a

(A) A hydroxylated polyethylene amine having at least 3 amino nitrogenatoms and not more than 6 amino nitrogen atoms and having 2 hydroxyalkylradicals attached to each of the 2 terminal amino nitrogen atoms andwith the proviso that'at least 1 of the intermediate nitrogen atoms bepart of a secondary amino group; and

(B) At least 1 mole of a high molecular weight monocarboxy acid havingat least 8 carbon atoms; said polymerized condensation productcontaining a plurality of Me ca each other.

MEIMEN DE GROO'IE.

